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WO2022117421A1 - Production d'acétonitrile à partir d'ammoniac et de méthanol - Google Patents

Production d'acétonitrile à partir d'ammoniac et de méthanol Download PDF

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Publication number
WO2022117421A1
WO2022117421A1 PCT/EP2021/082934 EP2021082934W WO2022117421A1 WO 2022117421 A1 WO2022117421 A1 WO 2022117421A1 EP 2021082934 W EP2021082934 W EP 2021082934W WO 2022117421 A1 WO2022117421 A1 WO 2022117421A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
metal
process according
acetonitrile
mol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP2021/082934
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English (en)
Inventor
Kasper Rode NIELSEN
Thoa Thi Minh NGUYEN
Philip MALCHO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topsoe AS
Original Assignee
Haldor Topsoe AS
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Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of WO2022117421A1 publication Critical patent/WO2022117421A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
    • C07C255/03—Mononitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres

Definitions

  • Embodiments of the invention generally relate to a process for selectively producing a product gas comprising acetonitrile from a feed stream comprising ammonia and methanol in the presence of a solid catalyst and a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol.
  • Aliphatic nitriles are important starting materials for polymers as well as for the synthesis of e.g., pharmaceuticals and pesticides. Nitriles are additionally good solvents for both polar and nonpolar solutes.
  • Nitriles may be produced by reaction of nitrogen-free precursors (such as alkanes, olefins, alcohols, aldehydes, or acids) with ammonia.
  • nitrogen-free precursors such as alkanes, olefins, alcohols, aldehydes, or acids
  • gas phase reaction of olefins with ammonia in the presence of oxygen (ammoxidation) and oxidation catalysts has attained the greatest industrial importance for the production of acrylonitrile from propene and methacrylonitrile from isobutene.
  • This process is known as the SOHIO process.
  • the vast majority of acetonitrile is produced as a by-product of the SOHIO process.
  • the SOHIO process is an ammoxidation of propylene (or more recently propane) to yield acrylonitrile.
  • the process takes place in a fluidized bed at 400-510 °C and BO- OO kPa gauge.
  • the catalysts employed are si
  • Acetonitrile is only available as a by-product from the synthesis of acrylonitrile. So far there is no commercial process dedicated for producing acetonitrile.
  • the ratio of hydrogen cyanide by-product and acetonitrile in the product stream can be controlled by the ratio of a first metal and a second metal in a bimetallic catalyst. This is advantageous in that it ensures a minimum production of hydrogen cyanide and syngas by-products.
  • An aspect of the invention provides a process for producing selectively acetonitrile comprising reacting a feed stream comprising methanol and ammonia in the presence of a bimetallic catalyst comprising a support, and a first metal selected from Fe, Ni, Co and a second metal selected from Sn, Zn, Ge, wherein the first metal is present in an amount of between 1 and 35 weight %.
  • the support comprises oxide of aluminum or spinel of aluminum.
  • the first metal is Co and the second metal is Sn.
  • the mol ratio of the first and the second metal is preferably between 0.5 and 5.
  • the molar ratio of Co/Sn is between 2 and 3 and calcining the catalyst in a hydrogen containing atmosphere .
  • the molar ratio of Co/Sn is 1 and calcining the catalyst in air.
  • the mol ratio of methanol to ammonia in the feed to the reactor is between 0.1 and 10.
  • the feed stream is reacted at a temperature of between 400 and 700 °C.
  • the bimetallic catalyst is subjected to a heat treatment in a hydrogen containing atmosphere prior to the reacting of the feed stream, preferably at a temperature of between 400 and 1000 0 C.
  • the catalyst has been subjected to a heat treatment in an atmosphere containing oxygen prior to the reacting of the feed stream, preferably at a temperature of between 400 and 1000 °C.
  • the process according to the invention is carried out at ambient pressure or higher.
  • Another aspect of the invention relates to a catalyst for catalyzing reactions producing selectively acetonitrile from a feed stream comprising ammonia and methanol, the catalyst comprising a support, a first metal and a second metal on the support, wherein the first metal is Fe, Ru or Co, and where the second metal is Sn, Zn or Ge and wherein the first metal is present in an amount of between 1 and 35 weight %.
  • the support comprises oxide of aluminum or spinel of aluminum.
  • the first metal is preferably Co and the second metal is Sn, the mol ratio of the first and the second metal is preferably between 0.5 and 5.
  • the catalyst is subjected to a heat treatment in an atmosphere containing hydrogen, preferably at a temperature between 400 and 1000 0 C.
  • the catalyst is subjected to a heat treatment in an atmosphere containing oxygen, preferably a temperature between 400 and 1000 0 C.
  • the final catalyst had a Co content of 4.75 wt% and an Sn content of 13.8 wt%, giving a Co/Sn ratio of 0.69 mol/mol.
  • This catalyst was denoted Co5Snl5-6O.
  • the final catalyst had a Co content of 4.65 wt% and an Sn content of 9.31 wt%, giving a Co/Sn ratio of 1.01 mol/mol.
  • This catalyst was denoted Co5SnlO-60.
  • the final catalyst had a Co content of 4.83 wt% and an Sn content of 5.24 wt%, giving a Co/Sn ratio of 1.84 mol/mol.
  • This catalyst was denoted Co5Sn5-6O.
  • the final catalyst had a Co content of 4.97 wt% and an Sn content of 3.66 %, giving a Co/Sn ratio of 2.66 mol/mol.
  • This catalyst was denoted Co5Sn3-6O.
  • examples 5-8 the same raw materials as in examples 1-4 were used. However, instead of calcining 20 g at 600 °C air, 4 g of the materials were treated at 600 °C for 2 hours in a flowing atmosphere comprising 2 vol% H2 in Ar.
  • Examples 9-12 have been prepared the same way as in examples 5-8 but instead of treating the catalysts at 600 °C in 2 vol% H2 in Ar for 2 hours, the catalysts were treated at 800°C in 2 vol% H2 in Ar for 2 hours.
  • the tests were performed in three steps each having a total flow of reactants of 50 Nml/min and a temperature of 550 °C.
  • the first step had a methanokammonia molar ratio of 1.4
  • the second step had a methanokammonia molar ratio of 2.6
  • the third step had a methanokammonia molar ratio of 3.8 - with N2 being added as an inert gas.
  • Fig.l summarizes the results from the second step for the 4 catalysts described in examples 1-4.
  • Fig.2 shows the effluent concentrations of HCN and acetonitrile for Co5SnlO-60 and Co5Sn5-6O, respectively, for each step in the test procedure described in example 13.
  • Reaction conditions Amount of catalyst: 300 mg, total flow: 50 Nml/min (N2, NH3 and CH3OH), temperature: 550 °C.
  • the catalysts prepared according to examples 5-8 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
  • ACN acetonitrile
  • HCN hydrogen cyanide
  • the catalysts prepared according to examples 9-12 were heated to 550 °C in 50 Nml/min N2 and tested similarly to the procedure described in example 13.
  • the trends are the same as for the catalysts treated at 600 °C in Fh/Ar but this time the acetonitrile concentration was higher for all the samples and this was also true for the total nitrile concentration.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé et un catalyseur pour la production sélective d'acétonitrile comprenant la réaction d'un courant d'alimentation comprenant du méthanol et de l'ammoniac en présence d'un catalyseur bimétallique comprenant un support, et un premier métal choisi parmi Fe, Ni, Co et un second métal choisi parmi Sn, Zn, Ge, le premier métal étant présent en une quantité comprise entre 1 et 38 % en poids et le second métal en une quantité comprise entre 1 et 38 % en poids.
PCT/EP2021/082934 2020-12-02 2021-11-25 Production d'acétonitrile à partir d'ammoniac et de méthanol Ceased WO2022117421A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA202001366 2020-12-02
DKPA202001366 2020-12-02

Publications (1)

Publication Number Publication Date
WO2022117421A1 true WO2022117421A1 (fr) 2022-06-09

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PCT/EP2021/082934 Ceased WO2022117421A1 (fr) 2020-12-02 2021-11-25 Production d'acétonitrile à partir d'ammoniac et de méthanol

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20250281878A1 (en) * 2023-10-31 2025-09-11 Carbon Utility LLC Process for producing a carbon product and carbon fibers through a carbon neutral or carbon negative process

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB792575A (en) * 1954-06-25 1958-04-02 Union Carbide Corp Production of nitriles
EP1366019B1 (fr) * 2001-03-05 2009-11-25 Ineos Usa Llc Ammoxydation d'un melange d'alcools en un melange de nitriles, en particulier en acetonitrile et hcn
US20140148610A1 (en) * 2012-11-26 2014-05-29 Ineos Usa Llc Pre calcination additives for mixed metal oxide ammoxidation catalysts
US20190009252A1 (en) * 2016-01-09 2019-01-10 Ascend Performance Materials Operations Llc Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream
EP3577073A1 (fr) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production d'acétonitrile et/ou de cyanure d'hydrogène à partir d'ammoniac et de méthanol

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB792575A (en) * 1954-06-25 1958-04-02 Union Carbide Corp Production of nitriles
EP1366019B1 (fr) * 2001-03-05 2009-11-25 Ineos Usa Llc Ammoxydation d'un melange d'alcools en un melange de nitriles, en particulier en acetonitrile et hcn
US20140148610A1 (en) * 2012-11-26 2014-05-29 Ineos Usa Llc Pre calcination additives for mixed metal oxide ammoxidation catalysts
US20190009252A1 (en) * 2016-01-09 2019-01-10 Ascend Performance Materials Operations Llc Catalyst compositions and process for direct production of hydrogen cyanide in an acrylonitrile reactor feed stream
EP3577073A1 (fr) * 2017-02-06 2019-12-11 Haldor Topsøe A/S Production d'acétonitrile et/ou de cyanure d'hydrogène à partir d'ammoniac et de méthanol

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20250281878A1 (en) * 2023-10-31 2025-09-11 Carbon Utility LLC Process for producing a carbon product and carbon fibers through a carbon neutral or carbon negative process

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